TW201936506A - Flaky titanate, method for producing same, and uses thereof - Google Patents

Abstract

Provided are a flaky titanic acid that exhibits a high weathering resistance while at the same time having the ability to endow a coating film with a silky presentation having a shading sensation and a strong brilliance, and a method for the production thereof suitable at least for inexpensive industrial production. The flaky titanic acid contains a basic organic compound wherein the content of basic functional groups thereof is not more than 2.4%, and provides a coating film having a goniometric color measurement value [Delta]L* of at least 150. The method for producing a flaky titanic acid contains a step of classifying a flaking titanic acid having a basic organic compound at the surface and/or in interlayer position, to bring (D90-D10)/D50 in the volume-based particle size distribution to 1.5 or less.

Description

Flaky titanic acid, its production method and use thereof

The present invention relates to a flaky titanic acid, a method for producing the same, and a use thereof, and more particularly to a bright pigment, a dispersion, and a resin composition containing the flaky titanic acid.

As a designing property to the surface of an article, a glittering coating film containing a bright pigment is known. Conventionally, a bright pigment having a titanium oxide layer is provided on the surface of a scaly substrate such as natural mica, synthetic mica or scaly alumina, and is used in many fields. These conventional bright pigments have a bright feeling (the so-called bright feeling refers to the brightness of the metallic hue) and have a particle sensation (the so-called particle sensation refers to a design in which the particles are individually glittering). It is used as a pigment which imparts pearl luster to a coating film.

In recent years, as a design with a higher sense of quality, the proposal has a denser sense of dense brightness that gives a deeper calm than the pearl luster and suppresses the sense of the particles (the so-called dense feeling means that there is no connection like a dragonfly. The smooth design of the seam), that is, the design of the silky feel. As a glittering pigment which can impart such a silky feeling, flaky titanic acid is known.

For example, Patent Document 1 discloses a bright pigment which treats a layered titanate with an acid, and secondly, an alkaline organic compound which acts to swell or peel off the flaky titanic acid between the layers, and The flaky titanic acid has an average major axis of 5 to 30 μm and an average thickness of 0.5 to 300 nm.

Further, in Patent Document 2, the applicant also proposes a coating film having a soft white-silver metal, which is flaky titanic acid used as a bright pigment, and which is smooth and has a high texture. Specifically, it is described that a raw material mixture is fired at a relatively high temperature to obtain a metal titanate, the metal titanate is treated with an acid, and then an alkaline organic compound is allowed to act, and the layers are peeled off to form a sheet. The average long diameter of the face is larger than 35 μm, and at least the flaky titanic acid having an alkaline organic compound on the surface.

Patent Document 3 discloses a flaky titanic acid suspension useful for the formation of a hard coat film. In this document, it is described that the layered titanate metal salt is treated with an acid or the like, and then, the basic compound having an interlayer swelling action acts, and after the layers are separated, the pH of the liquid is adjusted to a range of 6 to 9.

Patent Document 4 discloses a dispersion of a titanate nanosheet having excellent transparency. In this document, it is described that a dispersion of an alkali-containing titanium titanate sheet is brought into contact with a cation exchange resin.
[Previous Technical Literature]
[Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication No. 2006-257179
[Patent Document 2] Japanese Patent Laid-Open Publication No. 2013-184883
[Patent Document 3] Japanese Patent Laid-Open Publication No. 2006-206841
[Patent Document 4] Japanese Patent Laid-Open Publication No. 2008-247712

[Questions to be solved by the invention]

However, in recent years, a coating film having a unique design feeling that has not been hitherto has been sought, and a bright pigment which can be realized by this is being sought. Specifically, a pigment is sought, which is capable of imparting a coating film having a glossy feeling and a silky feeling with a shadow (that is, a low particle feeling and a high denseness), and can be displayed even if it is a coating film. Highly weatherable bright pigments are available for practical use at industrial production.

The present applicant has improved the technique of the applicant described above, and has acted on an alkaline organic compound to promote the peeling of the layered titanic acid, and to produce a flaky titanic acid having a thickness within a certain range, and it is confirmed that the bright feeling is strong and has The silky feeling of the shadow is imparted to the film. On the other hand, it has also been confirmed that there is a problem that the weather resistance of the coating film is remarkably lowered.

Patent Document 1 describes that the alkaline organic compound remaining between the layers is reduced by cerium ions, thereby suppressing discoloration of the coating film. However, bismuth compounds are expensive, so it is difficult to say that they are suitable for industrial production. Further, although the average long diameter or the average thickness is described, there is no description about the particle size distribution, and no disclosure of the method for adjusting the particle size distribution. There is also no disclosure of the effect of the particle size distribution on the weatherability or design of the coating film.

In Patent Document 2, by using a small amount of the basic organic compound, the peeling of the layered titanic acid is reduced, and the flaky titanic acid is relatively thickened to obtain a metallic white color which imparts a soft white color to the coating film. Glossy flaky titanic acid. This technique has been intended to have a different hue than the bright pigment of the present invention, and the shadow or the glare is low. Further, the amount of the remaining basic organic compound was a certain amount or more, and the weather resistance was insufficient, and when it was used for a long period of time outside the house, yellowing of the coating film was observed.

In Patent Document 3, it is described that the pH of the flaky titanic acid suspension is set to 6 to 9 by acid neutralization, whereby the light resistance of the titanic acid film can be improved, and discoloration can be suppressed. However, this technology is aimed at hard coaters excellent in transparency and the like, and is seeking not to impart gloss. Further, this method is effective in improving the weather resistance of a film having a relatively thin flaky titanic acid such as brightness.

In Patent Document 4, it is described that an amine which is a cause of discoloration of a resin or the like can be reduced by bringing a dispersion of an anion-containing nanocrystalline titanate sheet into contact with a cation exchange resin. However, this technique is also different from the functionally required function of the glittering coating film for a functional film of a titanate nanosheet excellent in transparency and the like. Further, this method is effective in improving the weather resistance of a film having a relatively thin flaky titanic acid such as brightness.

[Means to solve the problem]

The present inventors conducted an effort to study in view of the problems of the prior art described above. Further, it has been found that by blending the amount of the basic functional group into a specific range, when blending on the coating film, it is determined that the variable angle color measurement value shows a specific range of flaky titanic acid, and/or the particle size distribution is specified. The scope can solve the above problems and complete the present invention.

That is, the present invention encompasses the invention described below.
(1) A flaky titanic acid comprising an alkaline organic compound,
The basic functional group content is 2.4% or less,
The variable angle color measurement value ΔL ^* ₁ at the time of coating is 150 or more.
(2) A flaky titanic acid comprising an alkaline organic compound,
The basic functional group content is 2.4% or less,
The variable angle color measurement value ΔL ^* ₂ when the film is applied is 60 or more.
(3) A flaky titanic acid, which is a volumetric particle size distribution measured by a laser diffraction/scattering method, and the cumulative 10% particle diameter is represented by D10, and the median diameter is represented by D50, which will accumulate 90% of the particle diameter. When expressed by D90, (D90-D10)/D50 is 1.5 or less.
(4) A method for producing a flaky titanic acid, which comprises grading a flaky titanic acid having an alkaline organic compound which is present between layers and/or surfaces, and is classified in a volume particle size distribution (D90-D10)/D50 It is a step of 1.5 or less.
(5) A method for producing a flaky titanic acid, which comprises the step of separating a layer of a layer of titanic acid having a (D90-D10)/D50 of 1.5 or less with a basic organic compound in a volume particle size distribution.
(6) A method for producing a flaky titanic acid, comprising the step of obtaining a layered titanic acid by contacting a metal salt of a titanate having a (D90-D10)/D50 of 1.5 or less with an acidic compound in a volume particle size distribution And a step of separating the layer of the above-mentioned layered titanic acid with a basic organic compound.
(7) The method for producing a flaky titanic acid according to any one of (4) to (6) further comprising a flaky titanic acid containing an alkaline organic compound present in the interlayer and/or the surface The step of the aqueous medium having a pH of 6 or more and less than 10.
(8) A bright pigment comprising the flaky titanic acid according to any one of (1) to (3).
(9) A dispersion containing at least the flaky titanic acid according to any one of (1) to (3) and a dispersion medium.
(10) A resin composition comprising at least the flaky titanic acid and the resin according to any one of (1) to (3).
(11) A coating composition comprising at least the flaky titanic acid and a resin according to any one of (1) to (3).
(12) A plastic resin composition comprising at least the flaky titanic acid and the plastic resin according to any one of (1) to (3).
(13) An ink composition comprising at least the flaky titanic acid according to any one of (1) to (3), a resin, and a solvent.

[Effect of the invention]

According to the present invention, it is possible to provide a flaky titanic acid which is excellent in glossiness and has a silky feeling of a shadow, and which exhibits high weather resistance, and which is inexpensive and suitable for industrial production. Further, it is possible to further impart a smooth feeling to the coating film by improving the dense feeling and reducing the feeling of the particles. Accordingly, the flaky titanic acid of the present invention is suitably used as a bright pigment, and can be blended in a coating composition, an ink composition, a plastic resin composition or the like. Thereby, it is possible to provide an article having a unique design feeling that has not been used in the past.

The present invention relates to a flaky titanic acid comprising a basic organic compound having a basic functional group content of 2.4% or less, and a variable angle color measurement value ΔL ^* ₁ as a coating film of 150 or more. Or a flaky titanic acid having a basic functional group content of 2.4% or less, and a variable angle color measurement value ΔL ^* ₂ as a coating film of 60 or more.
In this way, the "titanic acid" of the flaky titanic acid of the present invention is a composition which is generally referred to as "titanic acid" composed of Ti and O and H atoms, and further contains an alkaline organic compound. Titanic acid (also known as "titanate composition"). Therefore, the flaky titanic acid of the present invention may be referred to as a "flaky titanic acid composition" in order to distinguish it from the general "titanic acid" composition composed of Ti and O and H atoms.
In addition, the form of the flaky titanic acid (flaky titanic acid composition) of the present invention can be used for the purpose of the invention, and examples of the particles include a form of a powder and a form of a solution (specifically, The flaky titanic acid of the present invention is used as a dispersion of particles dispersed in a dispersion medium (that is, a form called "dispersion"), as a bulk form or the like.

Although titanic acid is known to have various crystal structures, it is suitable to use a titanic acid having a layered crystal structure.

Various crystal structures exist in the titanic acid having a layered crystal structure. The crystal form is different from the crystallographic type A (anatase type) or R type (rutile type) titanium oxide. As the titanic acid having a layered crystal structure, for example, a porphyrin-consisting TiO ₆ octahedron can be used, and a sheet having a quaternary diffusion in the a-axis and the c-axis direction can be used, and a ferritic laminated structure having a cation can be used. A titanic acid having a layered crystal structure of a mineral structure. The crystal structure can be confirmed by powder X-ray diffraction.

In the present invention, the term "sheet" refers to the shape of the titanic acid particles, and includes a concept called a plate shape, a sheet shape, a flake shape, and a scale shape, and is compared with the ratio of the width to the length of the thickness. The shape of the big.

The flaky titanic acid of the present invention contains a basic organic compound, and the content of the basic functional group of the basic organic compound is 2.4% or less by the following formula. The flaky titanic acid obtained by swelling and/or exfoliating the layer of the titanic acid having a layered crystal structure with a basic organic compound contains an alkaline organic compound on both the surface and the interlayer. The basic functional group in which the basic organic compound is present has any effect on the titanium-oxygen unit, and is considered to be one of the reasons for the decrease in weather resistance of the coating film containing flaky titanic acid. When the content of the basic functional group derived from the basic organic compound is 2.4% or less, the deterioration of the weather resistance of the coating film containing the flaky titanic acid can be reduced. The content thereof is preferably 2.1% or less, more preferably 2.0% or less, still more preferably 1.7% or less, and still more preferably 1.3% or less. The lower limit of the basic functional group content is not particularly limited, and the smaller the better, the basic functional group derived from 0.01% or more of the basic organic compound is usually contained. The content of the basic functional group is determined by the following calculation formula by the amount of carbon (% by mass) measured by CHN analysis.
Basic functional group content (%) = (number of basic functional groups per molecule of basic organic compound) × (carbon amount (% by mass)) / {(amount of atomic carbon × number of carbon atoms per compound) / (quantity of TiO ₂ )}
(In the formula, the atomic weight of carbon is set to 12.0, and the amount of TiO ₂ is 79.9. When the basic organic compound is a polymer, the monomer constituting the monomer is regarded as one molecule, and the number of carbon and the basic functional group are determined. Calculated by number).

Examples of the basic organic compound include (1) a quaternary ammonium hydroxide compound (tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, etc.), ( 2) an alkylamine compound (propylamine, diethylamine or the like), (3) an alkanolamine compound (ethanolamine, aminomethylpropanol, etc.) or the like.

The flaky titanic acid of the present invention has a variable angle colorimetric value ΔL ^* ₁ of 150 or more measured under the following conditions on a coating film produced under the following conditions. The variable angle color measurement value ΔL ^* ₁ means that the L ^* value of the bright spot of the incident light (-45°) is set to be 0° with respect to the normal direction of the coating film surface (L of the light receiving angle of 40°) ^* value of the light receiving angle of 50 ° among the L ^* value of greater value) and shadow (L light-receiving angle -65 °) difference between the value of ^*. ΔL ^* ₁ has been reflected by the visual shadow, and the larger the ΔL ^* _{1, the} more the shadow of the coating film feels stronger. The variable angle color measurement value ΔL ^* _{1 is} preferably 160 or more, more preferably 170 or more. The upper limit of ΔL ^* ₁ is not particularly limited, but it is sufficient if it is 200 or less.

The variable angle color measurement value ΔL ^* ₁ of the coating film was determined as follows. First, a coating containing flaky titanic acid was produced. As shown in Table 1, an acrylic ruthenium resin blend was prepared by weighing a resin, an additive, and a solvent and dispersing it for 5 minutes with a paint shaker. 1.25 g of a pigment, 11.9 g of a ruthenium acrylate resin blend, and 9.40 g of pure water were placed in a glass container, and mixed with a paint shaker for 5 minutes to prepare a paint. The coating film thus prepared was applied to a PET film by a 3 mil blade, and then forcedly dried at 60 ° C for 30 minutes to prepare a coating film. In the coating film thus produced, the black background of the black and white chart paper is faced to the back side, and the incident light is irradiated from -45° using a variable angle spectrophotometric system (manufactured by Murakami Color Research Co., Ltd., GCMS-3 type). L ^* values for bright points (light angles of 40° and 50°) and shadows (light angles of -65°). Subtracting from the maximum value of the shading highlights the L ^* value L ^* value, defined as the displacement angle of the coating film colorimetric values ΔL ^* _1.

The flaky titanic acid of the present invention has a variable angle colorimetric value ΔL ^* ₂ measured by the following conditions different from those described above under the following conditions. The variable angle color measurement value ΔL ^* ₂ refers to the L ^* value (light receiving angle of 30°) and the shadow (for the light receiving angle of 30°) for the incident light (-45°) when the normal direction of the coating film surface is set to 0°. The difference in the L ^* value of the acceptance angle -65°). ΔL ^* _{2 is} also the same as the above-mentioned ΔL ^* _1, which reflects the visual shadow, and the larger the ΔL ^* _{2, the} more the shadow of the coating film feels stronger. The variable angle color measurement value ΔL ^* _{2 is} preferably 65 or more, more preferably 70 or more. The upper limit of ΔL ^* ₂ is not particularly limited, but it is sufficient if it is 90 or less.

The variable angle color measurement value ΔL ^* ₂ of the coating film was determined as follows. First, a coating containing flaky titanic acid was produced. As shown in Table 1, an acrylic ruthenium resin blend was prepared by weighing a resin, an additive, and a solvent and dispersing it for 5 minutes with a paint shaker. Into a glass container, 5.0 g of a pigment and 11.9 g of a ruthenium acrylate resin blend were placed in a glass jar, and mixed with a paint shaker for 5 minutes, and then pure water was added so that the viscosity of the coating material became 200 mPa·s to prepare a paint. The coating film thus produced was applied to a PET film by a spray gun, and then forced to dry at 60 ° C for 30 minutes to prepare a coating film having a film thickness of 10 μm. In the coating film thus produced, the white background of the black and white chart paper was faced to the back side, and the light source was irradiated from the direction of -45° using a multi-angle colorimeter (BYK-mac i manufactured by Biggardner Co., Ltd.) to measure the bright spot (light receiving angle). L ^* value of 30°) and shadow (light-receiving angle -65°). Highlights of subtracting from the L ^* L ^* Shadow, as the displacement angle of the coating film colorimetric values ΔL ^* _2.

The thickness of the flaky titanic acid is increased to a certain thickness, and the value of ΔL ^* ₁ (or ΔL ^* ₂ ) is increased, that is, the shadow feeling is enhanced. On the other hand, when the thickness of the flaky titanic acid is too thin, the value of ΔL ^* ₁ (or ΔL ^* ₂ ) is smaller, that is, the shading feeling starts to decrease. When a thin flaky titanic acid having a thickness of ΔL ^* ₁ (or ΔL ^* ₂ ) as a sufficient range as described above is obtained, it becomes a basic organic compound which uses a large amount of a release agent at the time of its production, and the residual amount (basic functional group) The content is apt to increase, and as a result, the weather resistance is liable to decrease. The flaky titanic acid of the present invention can impart a strong shadow to the coating film while imparting high weather resistance by setting the content of ΔL ^* ₁ (or ΔL ^* ₂ ) and the basic organic functional group to a specific range.

The average thickness of the flaky titanic acid is preferably in the range of 0.05 to 0.4 μm, and more preferably in the range of 0.05 to 0.3 μm. A coating film containing flaky titanic acid was prepared by an average thickness, and the coating film was cut by a microtome, and the cross section thereof was observed by an electron microscope, and the thickness of 50 or more randomly selected particles was measured, and the measured values were averaged. .

The flaky titanic acid of the present invention is a volume particle size distribution measured by a laser diffraction/scattering method, and the cumulative 10% particle diameter is D10, the median diameter is D50, and the cumulative 90% particle diameter is determined. The value calculated by D90 is calculated from the volume particle size distribution, and the value calculated by the calculation formula (D90-D10)/D50 is used as an index. The measurement of the volume particle size distribution by the laser diffraction/scattering method is carried out by a wet method in which the flaky titanic acid of the present invention is dispersed as a dispersion of particles (flaky titanic acid particles) in a dispersion medium. The above calculation formula indicates an index of the sharpness of the particle size distribution of the flaky titanic acid. When the value is small, the particle size distribution is good, and when it is large, the particle size distribution is broad. It is preferable that the value calculated by the calculation formula (D90-D10)/D50 is 1.5 or less. Since the coarse particles have a large ratio (aspect ratio) in the longitudinal direction to the length in the thickness direction, the effect of improving the glittering feeling is enhanced, and the particle sensation is also enhanced, and the dense feeling is also lowered. As a result, when the ratio of the presence of the coarse particles is reduced, the coating film having a reduced particle feel and high denseness is obtained, but the lightness and the shadowiness are deteriorated. In this case, when the ratio of the presence of the fine particles is also reduced, the low-particle feeling and the high-density feeling can directly maintain the brightness and the shadow, and the weather resistance can be improved. (D90-D10)/D50 is preferably 1.2 or less. The measurement of the particle size distribution by the laser diffraction/scattering method of the flaky titanic acid was carried out using a laser diffraction/scattering particle diameter distribution measuring apparatus (manufactured by Horiba, Ltd., LA-950) to set the refractive index. 2.50 to carry out.

The specific particle size is not in the range of (D90-D10)/D50 which is larger than 1.5, and the totality consideration may be determined by the design feeling of the coating film or the level of weather resistance. For example, D10 is preferably 9 μm or more. As described above, when D10 is 9 μm or more, when the ratio of the fine particles of less than 9 μm is less than 10%, the film can be sufficiently reduced, and the lightness, the drop shadow, and the weather resistance can be suppressed. More preferably, D10 is 10 μm or more. D90 is preferably 65 μm or less. As described above, when the ratio of the coarse particles larger than 65 μm is less than 10%, the D90 is 65 μm or less, and the particle sensation of the coating film can be suppressed. The D90 is preferably 55 μm or less. In particular, D99 (accumulated 99% particle diameter) is preferably 110 μm or less, more preferably 90 μm or less, still more preferably 80 μm or less. When D99 is 110 μm or less, the ratio of the coarse particles larger than 110 μm may be less than 1%, and may be lowered. When D99 is 90 μm or less, the ratio of the coarse particles larger than 90 μm may be sufficiently reduced by less than 1%. The same as D90, the expression of the particle sensation of the coating film can be suppressed. D50 is preferably in the range of 10 to 40 μm, more preferably in the range of 10 to 30 μm.

The flaky titanic acid of the present invention may contain a nitrogen element. The content thereof may be 2 to 5% by mass. The nitrogen content can be determined by CHN analysis.

The flaky titanoic acid of the present invention may contain an alkali metal (lithium, sodium, potassium, rubidium, cesium), and may not be contained. Similarly to Patent Document 1, an alkali metal of about 20% by mass can be contained. In the total amount of the alkali metal content of the flaky titanic acid of the present invention, the flaky titanic acid is sufficient to have a weather resistance of at least 5% by mass, and may be 1% by mass or less. In particular, the content of cerium can be made 0.01% by mass or less. The content of the alkali metal can be confirmed by fluorescent X-ray analysis as a calculated value of M ₂ O/TiO ₂ (M is an alkali metal).

Next, in the description of the method for producing the flaky titanic acid of the present invention, the entire production method of the flaky titanic acid will be fully described.

First, a metal titanate salt is produced. The metal titanate is obtained by using a metal oxide or a compound which is decomposed into a metal oxide by heating, a compound which forms titanium oxide with titanium oxide or by heating, and these starting materials are mixed and calcined. Then, if necessary, it can be broken. Further, in order to obtain a uniform and single-phase metal titanate, it is preferred to carry out the above-mentioned mixing sufficiently to grind and mix the raw material powder in an automatic mortar or the like.

The metal titanate is preferably a mixed metal salt of titanic acid produced as follows. That is, the alkali metal oxides M ₂ O and M′ ₂ O (M, M′ are respectively different alkali metals) or decomposed by heating into individual compounds of M ₂ O and M′ ₂ O, and titanium dioxide Alternatively, a compound which produces titanium dioxide by heating is preferably produced by mixing and calcining at a molar ratio of M/M'/Ti from 3/1/5 to 3/1/11.

As the alkali metal oxide, at least one of lithium, sodium, potassium, rubidium, and cesium oxides can be used. Further, as a compound which is decomposed into an alkali metal oxide by heating, an alkali metal carbonate, a hydroxide, a nitrate, a sulfate or the like can be used. Among them, carbonates and hydroxides are preferred. In addition, examples of the compound which generates titanium oxide by heating include an organotitanium compound such as a titanium hydroxide or a titanyloxy compound such as titanic acid or orthotitanic acid. Among them, titanium hydroxide is preferred.

The titanate mixed alkali metal salt obtained above is preferably a part of the Ti ⁴⁺ seat in the main skeleton, and is substituted with an alkali metal ion different from the alkali metal of the layer to form a composition M _x [M' _{x / 3} Ti _{2 -x/3} ]O ₄ (wherein M and M' are different alkali metals, and x is 0.50 to 1.0), and a compound having a layered structure of an orthorhombic structure (a crystal structure of a pyrite type). The x in the composition formula can be controlled by changing the mixing ratio of the starting materials.

Although the baking temperature differs depending on the type of the metal titanate, it may be approximately 1050 to 1200 °C. In the present invention, it is preferred to set the temperature (the melting point of the metal titanate salt - 150 ° C) to the temperature below the melting point of the metal titanate. When the baking temperature is set to this range, the grain growth of the titanate metal salt is promoted, and the yield in the classification step can be improved. In particular, flaky titanic acid having a particle diameter (laser diffraction/scattering method) having a median diameter of 10 to 40 μm (preferably 10 to 30 μm) is easily obtained in a high yield. For example, when the alkali metal salt of titanic acid of M = K and M' = Li is mixed, the firing temperature is preferably set to 1050 to 1200 °C. The representative composition, that is, M = K, M' = Li and x = 0.8, more preferably from 1050 to 1200 ° C, still more preferably from 1100 to 1180 ° C. Other firing conditions, such as the temperature rise and fall, the firing time, and the firing environment, are not particularly limited, and may be appropriately set. Further, a so-called flux method in which a flux is added during firing can be used. In this case, the baking temperature can be lowered, and it can be set to 800 to 1200 °C. As a flux, sodium chloride is mentioned, for example.

Then, the titanate metal salt obtained in the above step is brought into contact with an acidic compound to produce a titanic acid compound having a layered crystal structure (hereinafter sometimes referred to as "layered titanic acid"). The acidic compound is preferably an aqueous acid solution. Specifically, for example, after suspending the metal titanate in an aqueous solvent, an aqueous acid solution is added to extract a metal ion (a metal ion in the ion-exchanged titanate metal salt and a cation in the acid) to form a layered layer. The method of titanic acid.

The aqueous acid solution may, for example, be an aqueous solution of an inorganic acid or an organic acid, and is not particularly limited. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, and the like. Examples of the organic acid include acetic acid, oxalic acid, and the like. The concentration can be adjusted arbitrarily. In the case of specifying from 0.5 to 6, it is preferred that the time required for the reaction is appropriate, and more preferably from 1 to 3.

Among the metal titanate salts, it is preferred to use the aforementioned titanic acid mixed alkali metal salt. The alkali metal ion represented by M and M' in the titanate mixed alkali metal salt is activated by an exchange reaction with other cations or by insertion of an organic substance. Therefore, when it is in contact with an acidic compound, the alkali metal ion of the (M) and the (M') in the main skeleton is exchanged with other cations in a short time, and when industrial production is carried out, the layered titanium can be efficiently obtained at a low production cost. acid. The combination of M and M' is preferably (M, M') = (potassium, lithium), (yttrium, lithium), (yttrium, lithium), and particularly preferably a combination of (potassium, lithium).

As a method of efficiently performing the reaction with the acidic compound, a mixed metal titanate salt and an acidic compound may be used as the acidic slurry, and then the suction filter such as a filter press or a Buchner funnel may be in the form of a block and directly sucked and passed. The method of fresh acid. Moreover, it is preferable to wash and remove excess acid by ion-exchange water etc. after contact and reaction with an acidic compound. Then, coarse separation or the like can be performed if necessary. Further, the step of bringing the titanate metal salt into contact with the acidic compound may be carried out several times.

As the layered titanic acid, it is preferred that the metal ion between the layers is replaced by hydrogen ions, and the composition of the Ti ⁴⁺ seat in the main skeleton is also substituted.
H _4x/3 Ti _2-x/3 O ₄・nH ₂ O
(wherein x is from 0.50 to 1.0, and n is from 0 to 2) represents a compound having a layered structure of orthorhombic crystals. It is not necessary to replace all of the metal ions with hydrogen ions, and metal ions may remain in the range in which the effects of the present invention are obtained.

By the aforementioned method, the M element can be substituted with hydrogen ions with high efficiency. Specifically, it may be 1% by mass or less, preferably 0.5% by mass or less, in terms of M ₂ O/TiO ₂ .

Next, the layered titanic acid obtained in the above step is brought into contact with a basic organic compound. Thereby, the alkaline organic compound is intercalated between the layers by the exchange reaction of the hydrogen ions contained in the layered titanic acid with the basic organic compound to obtain a flaky titanic acid which swells and/or peels off at least a part of the layer. The method for making the contact is not particularly limited, and any method can be employed. In particular, it is preferred because the layered titanic acid is in contact with the basic organic compound in the vehicle liquid.

The order of addition of the layered titanic acid and the basic organic compound of the vehicle liquid is not particularly limited. For example, a layered titanic acid and a basic organic compound may be added to the vehicle to be stirred and mixed. Alternatively, a basic organic compound may be added to the slurry in which the layered titanic acid is dispersed in the vehicle. Alternatively, the layered titanic acid may be added to the alkaline organic compound solution.

In contact, apply external force if necessary. When an external force is applied, swelling and/or peeling between the layers of the layered titanic acid is facilitated. As a method of applying the external force, for example, a method of stirring a vehicle containing a layered titanic acid and a basic organic compound can be mentioned. In this case, the stirring conditions may be appropriately set. As a method of applying a force other than stirring, it is sufficient to vibrate the container of the vehicle. Vibrating screens, paint conditioners, oscillators, etc. can be used for the vibration. The vibration conditions in this case can also be set as appropriate.

The vehicle liquid is not particularly limited, and any vehicle can be used. Specifically, an organic solvent such as water or alcohol or a mixture of the above may be mentioned. Industrially, it is preferred to use an aqueous medium containing water as a main component.

The basic organic compound is not particularly limited, and one or two or more kinds of basic organic compounds can be appropriately selected and used. Specific examples thereof include (1) a quaternary ammonium hydroxide compound (tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, etc.), and (2) an alkane. a base amine compound (propylamine, diethylamine, etc.), (3) an alkanolamine compound (ethanolamine, aminomethylpropanol, etc.), and the like. Among them, an alkanolamine compound is preferably used, and an aminomethylpropanol is more preferably used. (1) The swelling and/or peeling between the layers of the layered titanic acid is relatively fast. (2) The swelling and/or peeling between the layers of the layered titanic acid is relatively slow. (3) Probably the middle.

The temperature at which the contact is made is not particularly limited and can be appropriately set. When the reaction temperature is set to room temperature (20 to 30 ° C), it is preferred because it is easy to adjust the peeling state. The reaction rate is also not particularly limited and can be appropriately set. The layered titanic acid can be mixed with the basic organic compound in one time, or can be mixed little by little, and can be mixed little by little. The reaction time is also not particularly limited, and may be appropriately set depending on the reaction temperature and the intended swelling and/or peeling state. For example, when the reaction temperature is 20 to 30 ° C, it is preferably about 30 minutes to 12 hours. The higher the temperature, the more continuous or intermittent the mixture, and the longer the time, the easier it is to swell and/or peel between the layers of the layered titanic acid.

The amount of the basic organic compound to be contacted with the layered titanic acid is preferably in the range of 0.01 to 10 neutralizing equivalents with respect to the hydrogen ion contained in the layered titanic acid. When the amount of the basic organic compound is too small, the hydrogen ions are not sufficiently removed, and the peeling cannot be performed. On the other hand, the larger the amount of the basic organic compound, the easier the swelling and/or peeling between the layers of the layered titanic acid is. When the amount is too large, the peeling between the layers becomes difficult due to swelling, and therefore the above range is preferable.

The concentration of the layered titanic acid in the vehicle liquid is preferably from 1 to 20% by mass, more preferably from 3 to 15% by mass, even more preferably from 5 to 15% by mass. The lower the concentration, the easier the swelling and/or peeling between the layers of the layered titanic acid is. On the other hand, the higher the concentration, the higher the production efficiency, so the above range is preferable.

The degree of peeling of the layered titanic acid compound can be adjusted by appropriately setting the type and amount of the basic organic compound to be used, the concentration of the layered titanic acid, and the intercalation between the layers of the cationic species for suppressing the peeling. The temperature, speed or time of contact, the method of applying an external force, or the degree of external force are performed. Thereby, the thickness of the obtained flaky titanic acid can be adjusted to a desired thickness. Also, maintain its dispersion stability.

In this way, a flaky titanic acid dispersion can be obtained. Further, for example, the flaky titanic acid can be obtained as a solid component by the following method.

For example, a solid component can be obtained by solid-liquid separation of flaky titanic acid from the above flaky titanic acid dispersion. A known filtration method can be used for the solid-liquid separation, and for example, a filtration device such as a rotary press or a filter press which is generally used in the industry can be used. At this time, if necessary, it can be washed to remove soluble salts and the like. Then, if necessary, dry it. In the washing, for example, pure water can be used. Any device can be used for drying, and the drying temperature and time can be appropriately set. The drying temperature is preferably 50 to 300 ° C, more preferably 100 to 300 ° C.

Alternatively, the above-mentioned flaky titanic acid dispersion liquid may be freeze-dried as a freeze-dried product to obtain a solid component. A freeze dryer can be used in freeze drying. The resulting freeze-dried material can continue to sublime the ice under vacuum.

Alternatively, the above flaky titanic acid dispersion is centrifuged, and the precipitate and the vehicle are separated and dried to obtain a solid component. A centrifugal separator can be used for the centrifugal separation. The centrifugation can be repeated more than 2 times.

Alternatively, the above-mentioned flaky titanic acid dispersion can be spray-dried to obtain a solid component. A general spray dryer can be used for spray drying.

Alternatively, the above solid component fractionation method may be carried out in combination with a plurality of components to obtain a solid component. The washing and solid component fractionation can be carried out in a plurality of combinations.

The obtained solid component can be pulverized if necessary. The aforementioned known pulverizer can be used for pulverization. From the viewpoint of maintaining the shape of the flaky titanic acid (the size and size of the sheet surface), it is preferable that the pulverizing force is weaker. As such a pulverizer, for example, a hammer mill or a pin mill can be cited.

According to a second aspect of the present invention, there is provided a method for producing a flaky titanic acid comprising flaky titanic acid having an alkaline organic compound present between layers and/or on a surface, which is classified by a laser diffraction/scattering method. For the volume particle size distribution, the step of (D90-D10)/D50 is set to 1.5 or less.

As an aspect, for example, a method for producing flaky titanic acid, which is prepared or purchased as a flaky titanic acid having an alkaline organic compound between layers and/or on the surface, is classified and subjected to laser diffraction. The volume particle size distribution determined by the scattering method was set to (D90-D10)/D50 to be 1.5 or less.

In another aspect, a method for producing a flaky titanic acid, which comprises the steps of obtaining a metal titanate, and contacting the metal titanate with an acidic compound to obtain a layered titanic acid, is mixed. The layered titanic acid and the basic organic compound, the step of swelling and/or peeling off the layer of the layered titanic acid, and the layer obtained by the step of the above step are peeled and/or swelled between the layers and/or the surface contains the alkaline organic compound. The flaky titanic acid of the compound is a step of setting (D90-D10)/D50 to 1.5 or less in a volume particle size distribution measured by a laser diffraction/scattering method.

When the flaky titanic acid produced in this manner is measured by a laser diffraction/scattering method with a median diameter of about 10 to 40 μm (preferably about 10 to 30 μm), the coating film is blended as it is blended. Shadow or dense. Here, when the metal titanate having a size of several tens of μm is synthesized, since the particle size distribution is very broad, the particle size distribution of the finally obtained flaky titanic acid is also broad. Although it is known that the flux variation can be somewhat reduced by the use of a flux for the synthesis of a metal titanate, the particle size distribution is still broad, and in particular, the formation of coarse particles cannot be avoided. The present invention is an additional classification step in which (D90-D10)/D50 is set to 1.5 or less in a volume particle size distribution measured by a laser diffraction/scattering method.

It is preferable that the classification is such that the ratio of the existence of both the coarse particles and the fine particles is reduced, and when the volume particle size distribution measured by the laser diffraction/scattering method is (D90-D10)/D50 of 1.5 or less, a weather resistance can be provided. Excellent, non-particle-like coating with a unique silky feel. The aforementioned value is more preferably 1.2 or less.

The alkaline organic compound used as a release agent remains in the form of flaky titanic acid. The basic organic compound is considered to be partially contained as a cation between the layers of the flaky titanic acid, and a part is present on the surface of the flaky titanic acid particles. The inventors of the present invention found that the residual basic organic compound is mostly present on the surface of fine particles, and the finer the particles, the more the relative basic organic compound content tends to be. Further, by reducing the amount of fine particles by classification, the amount of the basic organic compound contained in the finally produced flaky titanic acid powder can be reduced, thereby reducing the content of the basic functional group and significantly improving the weather resistance of the coating film. Sex.

In addition, the coating film which uses such a flaky titanic acid as a bright pigment has a brighter feeling as a display, in addition to a shadow feeling and a dense feeling. This is considered to be because the fine particle has a low aspect ratio, and the effect of reducing the relative brightness of the fine particles by the scattering of the ends of the particles is reduced. For the same reason, the silky feeling of the coating film is also highly changed. The threshold and removal amount of the removed particles are in the volume particle size distribution measured by the laser diffraction/scattering method, and the range of (D90-D10)/D50 is not larger than 1.5, and the total consideration becomes a necessary coating film. The level of brightness or weather resistance and the yield may be determined. For example, the volume particle size distribution measured by the laser diffraction/scattering method of the flaky titanic acid after the end of the classification step is preferably classified so that D10 (accumulated 10% particle diameter) is 9 μm or more.

By reducing the coarse particles by grading, the particle shape of the coating film shape is remarkably reduced or reduced to such an extent that it is unrecognizable by visual observation. Here, the term "gradation of coarse particles" in the present specification is not limited to the operation of removing coarse particles and reducing the content ratio thereof by using only various sorting devices as will be described later, and also includes adjusting the sheet shape by the manufacturing process. External force added to the titanic acid (for example, the shearing force at the time of peeling of the layered titanic acid, the addition of the flaky titanic acid to the fractionation of the fine particles of the flaky titanic acid using the classifying device, and the flaky titanic acid dispersion The centrifugal force at the time of centrifugation or the shearing force at the time of spray drying of the flaky titanic acid dispersion, etc., reduces the coarse particles. Of course, the classification by the classification of the classification device and the intensity adjustment by the external force added by the flaky titanic acid can also be used in combination.
Thereby, it is possible to provide a coating film which not only has a strong shadow feeling and a high gloss feeling, but also has a unique silky feeling without particle feeling. The threshold value and removal amount of the removed particles are in the volume particle size distribution measured by the laser diffraction/scattering method, and the range of (D90-D10)/D50 is not larger than 1.5, and the total consideration becomes a necessary coating film. The level of the brightness and the yield can be determined. For example, the volume particle size distribution measured by the laser diffraction/scattering method of the flaky titanic acid after the end of the classification step can be classified so that D90 (accumulated 90% particle diameter) becomes 65 μm or less. In particular, classification is carried out so that D99 (accumulated 99% particle diameter) becomes 90 μm or less.

The classification using the classification device can be carried out wet or dry. The apparatus used for the classification is not particularly limited, and any classification device can be used. Examples of the wet classifier include a vibrating sieve, a gravity field classification (such as a thickener), and a centrifugal force field classification (liquid cyclone, etc.). Examples of the dry classifier include a vibrating screen, a centrifugal force field classification (dry cyclone, etc.), and an inertial force field classification (classifier, etc.). When the layered titanic acid is brought into contact with the basic organic compound, the layered titanic acid is peeled off and directly classified in a wet form, which is preferable because the step can be simplified.

The adjustment of the particle size distribution by the classification using the classifying means can be carried out by a known method. For example, it can be adjusted by the choice of the mesh distance of the screen. In addition, the supply speed of the sample, the residence time on the sieve, the vibration condition, and the like may be adjusted by setting appropriate conditions in accordance with the classification method to be employed.

For example, when grading by a wet sieving, a slurry as a classification target is introduced into a mesh hole of a larger side by using a slurry classifier (manufactured by ACO JAPAN Co., Ltd.), and can be classified into a net, Under the net. Secondly, by placing the slurry under the net into the mesh hole of the smaller side, it can be classified into the net and the net. In this way, a slurry which is classified into three levels is obtained (hereinafter, it may be described as "screening", "sieving in the sieve", and "sieving under the sieve"). These operations can also be carried out using a general vibrating screen. Any screen spacing screen can be used as long as the effect of the present invention can be obtained. The mesh distance of the sieve on the larger side can be, for example, 75 μm or less, preferably 53 μm or less, more preferably 45 μm or less. The mesh distance of the sieve on the smaller side can be, for example, 6 μm or more, preferably 10 μm or more, and more preferably 20 μm or more.

A third aspect of the present invention provides a method for producing a flaky titanic acid, which comprises a layer size distribution of (D90-D10)/D50 of 1.5 or less, which is measured by a laser diffraction/scattering method. A step of swelling and/or exfoliating between layers of titanic acid with an alkaline organic compound.
By using the volumetric particle size distribution of the layered titanic acid by laser diffraction/scattering method, the layered titanic acid dispersion is used to irradiate/scatter light with the above-mentioned "flaky titanic acid" laser The measurement of the volumetric particle size distribution of the method is carried out in the same manner, and the calculation of the particle diameter (D10, D50, D90, etc.) is also calculated from the particle diameter of the above-described laser diffraction/scattering method by "flaky titanic acid". The same way.

For example, a method for producing flaky titanic acid, which comprises preparing or purchasing layered titanic acid, classifying it, and measuring the volume particle size distribution by a laser diffraction/scattering method, (D90-D10)/ D50 is a step of 1.5 or less, and the step of swelling and/or peeling off the layered layered titanic acid layer with a basic organic compound.

As another aspect, for example, a method for producing flaky titanic acid, which is included in a volumetric particle size distribution measured by laser diffraction/scattering by fractionation, may be prepared or purchased (D90-D10)/D50. The layered titanic acid having a thickness of 1.5 or less is subjected to a step of swelling and/or peeling off the interlayer with an alkaline organic compound.

In another aspect, for example, a method for producing a flaky titanic acid, which comprises the steps of obtaining a metal titanate, and contacting the metal titanate with an acidic compound to obtain a layered titanic acid, may be mentioned. And classifying the layered titanic acid in a volumetric particle size distribution measured by a laser diffraction/scattering method, and setting (D90-D10)/D50 to 1.5 or less, mixing the classified layered titanic acid and basic organic a step of swelling, and/or stripping the layer of the layered titanic acid.

As described above, the amount of the basic organic compound (the basic functional group content) after the peeling tends to have a large amount of fine titanic acid particles, and the fine particles are reduced to improve the glittering feeling and the silky feeling. When the coarse titanic acid particles are small, the particle sensation is also the same. Therefore, when the ratio of the fine particles of the layered titanic acid to the coarse particles is small, for example, even in the case of classifying layered titanic acid, the effects of the present invention are obtained in the same manner.

The classification can be carried out in a wet manner or in a dry manner. When the titanate metal salt is brought into contact with an acidic compound to obtain a layered titanic acid and then directly classified in a wet form, the step can be simplified. The classifying device or the classifying method is not particularly limited and can be carried out by any method. For example, it can be carried out in the same manner as the classification of the flaky titanic acid having an alkaline organic compound between the layers and/or the surface described above.

The layered titanic acid can be classified, and the flaky titanic acid after swelling and/or peeling can be classified.

According to a fourth aspect of the present invention, there is provided a method for producing a flaky titanic acid, which comprises a volume particle size distribution measured by a laser diffraction/scattering method, and which has a (D90-D10)/D50 of 1.5 or less. The step of contacting the acid metal salt with the acidic compound to obtain a layered titanic acid, and swelling and/or peeling the layer of the above-mentioned layered titanic acid with the basic organic compound.
The volume fraction distribution of the metal titanate salt by the laser diffraction/scattering method is determined by using the dispersion of the metal titanate salt and the above-mentioned laser diffraction/scattering by the "flaky titanic acid" The measurement of the volumetric particle size distribution of the method is carried out in the same manner, and the calculation of the particle diameter (D10, D50, D90, etc.) is also calculated from the particle diameter of the above-described laser diffraction/scattering method by "flaky titanic acid". The same way.

For example, a method for producing a flaky titanic acid, comprising the step of obtaining a metal titanate, and classifying the titanate metal salt, and measuring the volume particle size distribution by a laser diffraction/scattering method, (D90-D10) /D50 is set to a step of 1.5 or less, contacting the classified metal titanate with an acidic compound to obtain a layered titanic acid, mixing the layered titanic acid with an alkaline organic compound, swelling and/or peeling the layer The step between the layers of titanic acid.

As described above, the amount of the basic organic compound (the basic functional group content) after the peeling tends to have a large amount of fine titanic acid particles, and the fine particles are reduced to improve the glittering feeling and the silky feeling. When the coarse titanic acid particles are small, the particle sensation is also the same. Therefore, when the ratio of the fine particles of the metal titanate to the coarse particles is small, for example, even in the case of classifying the metal titanate, the effects of the present invention are obtained.

The metal titanate can be classified, and the flaky titanic acid after swelling and/or peeling can be classified. Further, the metal titanate, the layered titanic acid, the swelling, and/or the exfoliated flaky titanic acid may be classified.

Prior to the classification step, the step of pulverizing the metal titanate, the layered titanic acid or the flaky titanic acid may be included. When such a large amount of particles contain coarse particles, the yield can be improved by pulverizing in advance. In this case, when the fine particles are excessively pulverized, it is preferred to appropriately adjust the pulverization conditions so as to increase the ratio of the particles in the target particle size range. It can be peeled off at the peeling step and pulverized.

The pulverization can be carried out in a wet manner or in a dry manner, and is not particularly limited. The pulverizing apparatus is also not particularly limited, and a known pulverizing apparatus can be selected and used in accordance with the desired pulverizing strength. For example, a wet pulverizer such as a vertical sand mill, a horizontal sand mill, or a ball mill, a pulverizer such as a hammer mill or a pin mill, a pulverizer such as a pulverizer, a jet mill, or the like can be used. Air jet mill, etc.

Further, in the classification step, as the coarse particles, the particles may be pulverized and mixed with the sieve. For example, a method for producing flaky titanic acid includes a step of grading and/or peeling off flaky titanic acid between layers, and a step of pulverizing the classified particles as coarse particles. Thereby, the yield can be improved. The classifying device or the classifying method is not particularly limited and can be carried out by any method. For example, it can be carried out in the same manner as the classification of the flaky titanic acid having an alkaline organic compound between the layers and/or the surface described above. The pulverization method or the pulverization apparatus is not particularly limited, and the pulverization apparatus described above can be arbitrarily selected.

Further, in the classification step, as the coarse particles, the pulverization may be performed on the sieve, and the classification step may be carried out. For example, a method for producing flaky titanic acid includes a step of grading and/or peeling off flaky titanic acid between layers, a step of pulverizing the classified particles as coarse particles, and re-grading the pulverized material. The sieve obtained by re-classification can be mixed with the original sieve. Thereby, the yield can be improved. The classifying device or the classifying method is not particularly limited and can be carried out by any method. For example, it can be carried out in the same manner as the classification of the flaky titanic acid having an alkaline organic compound between the layers and/or the surface described above. The pulverization method or the pulverization apparatus is not particularly limited, and the pulverization apparatus described above can be arbitrarily selected.

Further, it can be taken as a fine particle in the classification step as a part of the sieve, and mixed with the sieve. In addition, the ratio of the presence of the fine particles is increased, and the continuous weather resistance is also lowered, and the glossiness is also lowered. Therefore, the total consideration is necessary to determine the brightness of the coating film or the level and the yield of the weather resistance, and the like. The amount of mixing can be. Thereby, the yield can be improved.

Further, a part of the sieve may be taken as a coarse particle in the classification step, and it may be mixed again with the sieve. In addition, the ratio of the presence of the coarse particles increases, and the continuity of the particle sensation at the time of coating the film is enhanced. Therefore, the totality is considered to be the level of the brightness of the coating film and the yield, and the amount of remixing is appropriately determined. Just fine. Thereby, the yield can be improved.

In the method for producing a flaky titanic acid according to the present invention, it is preferable to further comprise a flaky titanic acid containing an alkaline organic compound between layers and/or a surface, which is present under an aqueous medium having a pH of 6 or more and less than 10 The steps. Or preferably, the step of contacting the layered titanic acid with the basic organic compound, swelling and/or stripping the layer of the layered titanic acid, and further comprising the step of presenting at a pH of 6 or higher and less than 10 The steps of the aqueous medium. The flaky titanic acid containing an alkaline organic compound between the layers and/or the surface may, for example, be a flaky titanic acid which is in contact with the layered titanic acid and the basic organic compound, and the basic organic compound is intercalated between the layers and swelled. And/or stripping at least a portion of the layer.

For example, by subjecting a titanate metal salt having a (D90-D10)/D50 of 1.5 or less to an acidic compound by fractional volume particle size distribution, a step of obtaining a layered titanic acid, and a layered titanic acid and a base are obtained. After the step of contacting, swelling, and/or peeling off the layer of the layered titanic acid, the organic compound may further include a step of being carried out under an aqueous medium having a pH of 6 or more and less than 10.

Or in the step of contacting the layered titanic acid having a (D90-D10)/D50 of 1.5 or less with the basic organic compound by grading the volume particle size distribution, swelling and/or peeling off the layer of the layered titanic acid Thereafter, the step of further presenting in the aqueous medium having a pH of 6 or more and less than 10 may be further included.

Or in the step of contacting the layered titanic acid with the basic organic compound, swelling and/or peeling off the layer of the layered titanic acid, and classifying the flaky titanic acid, in the volume particle size distribution, (D90-D10)/D50 After the step of 1.5 or less, the step of presenting in the aqueous medium having a pH of 6 or more and less than 10 may be further included.

Or after the step of contacting the layered titanic acid with the basic organic compound, swelling and/or peeling off the layer of the layered titanic acid, and performing the step of the aqueous medium having a pH of 6 or more and less than 10 Then, the classification can be carried out, and in the volume particle size distribution, the step of setting (D90-D10)/D50 to 1.5 or less is performed.

When the flaky titanic acid is present in an aqueous medium having a pH of the above range, the basic functional group content alone cannot be reduced to a level sufficient to exhibit sufficient weather resistance, but the combination classification step and the flaky titanic acid are used. When the pH is in the range of the aqueous medium in the above range, the amount of the residual basic organic compound can be further reduced by the synergistic effect. That is, the content of the basic functional group contained in the finally produced flaky titanic acid powder can be reduced, and the weather resistance of the coating film can be remarkably improved. The decrease in the content of the basic functional group is effective when the pH is set to less than 6, but when the pH is set to less than 6, the flaky titanic acid is agglomerated, and the design feeling when the film is formed is lowered. When the pH is 6 or more and less than 10, the design property and weather resistance of the coating film can be achieved by the combination with the classification step.

As a method of the flaky titanic acid in the aqueous medium having a pH of 6 or more and less than 10, for example, an aqueous solvent containing flaky titanic acid is brought into contact with an acidic compound to set the pH to 6 or more. Less than 10 methods. The acidic compound is not particularly limited, and an inorganic acid or an organic acid or the like can be used arbitrarily. Examples of the inorganic acid include hydrochloric acid and sulfuric acid, and examples of the organic acid include acetic acid and oxalic acid. These acidic compounds may be dissolved in water, and may be mixed with an aqueous solution containing flaky titanic acid as an acidic aqueous solution. The flaky titanic acid is preferably maintained for a certain period of time. For example, it is preferably maintained for 30 minutes or more. At the time of stirring, it is preferable to increase the removal efficiency of the basic organic compound. The temperature at this time is not particularly limited and can be arbitrarily set. For example, it can be set to 20 to 70 °C.

After the flaky titanic acid is present in an aqueous medium having a pH of 6 or more and less than 10, a step of washing the flaky titanic acid may be additionally added. For the washing, a known method can be used. For example, a solid material can be precipitated by a thickener, a decanter, a centrifugal separator or the like by using a filtration device such as a rotary press or a filter press to remove the supernatant. A method of washing solid ingredients. In particular, the method according to the above (after the step of bringing the layered titanic acid into contact with the basic organic compound, swelling and/or peeling off the layer of the layered titanic acid, the pH is 6 or more and less than 10 The step under the aqueous medium is followed by classification, and in the volume particle size distribution, the method of setting (D90-D10)/D50 to 1.5 or less is performed, and the flaky titanic acid is present at pH 6 or higher. After the water-based medium is over 10, when the classification operation is performed, since the slurry under the sieve due to the classification contains a large amount of the alkaline organic compound, the slurry is removed by the classification, and the cleaning effect is also obtained. The simplification of the steps is possible.

According to a fifth aspect of the invention, the flaky titanic acid bright pigment of the first invention is contained.

According to a sixth aspect of the invention, there is provided a dispersion of at least the flaky titanic acid of the first invention and a dispersion medium.

The dispersion medium is not particularly limited, and any solvent can be used. Specifically, an organic solvent such as water or alcohol or a mixture of the above may be mentioned. Industrially, it is preferred to use an aqueous medium containing water as a main component.

When an organic solvent is used, the type thereof can be appropriately selected depending on the use. In particular, in the case of an organic solvent having a dielectric constant of 5 or more, the flaky titanic acid is preferably dispersed, and more preferably an organic solvent having a dielectric constant of 10 or more. More preferably, it is selected from the group consisting of acetonitrile (dielectric ratio 37, boiling point 82 ° C), methanol (dielectric ratio 33, boiling point 65 ° C), dimethyl hydrazine (dielectric ratio 47, boiling point 189 ° C). , ethanol (dielectric rate 24, boiling point 78.3 ° C), 2-propanol (dielectric ratio 18, boiling point 82.5 ° C), N, N-dimethylformamide (dielectric ratio 38, boiling point 153 ° C), A Base group consisting of ethyl ethyl ketone (dielectric ratio 18.5, boiling point 80 ° C), 1-butanol (dielectric ratio 17.8, boiling point 118 ° C) and formamide (dielectric ratio 109, boiling point 210 ° C) At least one. Further, since the organic solvent is easy to dry at a low temperature, it is preferably a low boiling point, more preferably a boiling point of 200 ° C or less, still more preferably 150 ° C or less, and even more preferably 100 ° C or less. By.

In addition to the flaky titanic acid and the dispersion medium, the dispersion liquid of the present invention may contain a resin binder, a dispersant, and a surface conditioner (a leveling agent, a wettability improvement), without impairing the effects of the present invention. As a third component, various additives such as a reagent, a pH adjuster, an antifoaming agent, an emulsifier, a coloring agent, an extender, an antifungal agent, a hardening aid, and a tackifier, and a filler are used. Specific examples of the resin binder include (1) an inorganic binder (a) a polymerizable hydrazine compound (hydrolyzable decane or a hydrolyzate thereof or a partial condensate thereof, water glass, colloidal cerium oxide, organic (polyoxane, etc.), (b) metal alcohol oxides, etc.), (2) organic binders (alkyd resins, acrylic resins, polyester resins, epoxy resins, fluorine resins, modified A polyanthracene resin). Examples of the dispersant include (1) a surfactant ((a) anionic (carboxylate, sulfate, sulfonate, phosphate, etc.), (b) cationic (alkylamine, alkyl) Amine 4-grade ammonium salt, aromatic 4-grade ammonium salt, heterocyclic 4-grade ammonium salt, etc.), (c) amphoteric (betaine type, amino acid type, alkylamine oxide, nitrogen-containing heterocyclic type, etc.) (d) nonionic (ether, ether, ester, nitrogen, etc.), (2) polyoxyl dispersant (alkyl modified polyoxane, polyoxyalkylene modified Polyoxane, etc.), (3) phosphate dispersant (sodium phosphate, sodium pyrophosphate, sodium orthophosphate, sodium metaphosphate, sodium tripolyphosphate, etc.), (4) alkanolamines (amine group A) The surface conditioning agent controls the surface tension of the organic solvent dispersion to prevent defects such as shrinkage and crater, and examples thereof include an acrylic surface conditioner and ethylene. A surface conditioner, a polyfluorene-based surface conditioner, a fluorine-based surface conditioner, or the like.

The amount of the third component other than the flaky titanic acid or the dispersion medium can be appropriately adjusted. For example, when the above-mentioned surfactant, polyoxynoxy dispersant, phosphate dispersant or alkanolamine is used as the dispersant, The weight of the flaky titanic acid is preferably about 0.005 to 5.0% by mass, more preferably about 0.01 to 2.0% by mass. As the surface conditioning agent, the above-mentioned polyfluorene-based surface conditioning agent or the like can be used, and it is preferably about 0.005 to 5.0% by mass, and more preferably about 0.01 to 2.0% by mass, based on the weight of the flaky titanic acid.

In the production of the dispersion, the above materials are mixed to disperse the flaky titanoic acid. As the dispersion, a disperser such as a usual agitator, a colloid mill, a ball mill, a bead mill, a shaker, a paint conditioner, an oscillator, a disperser, or the like can be used. The order of mixing the aforementioned materials is not particularly limited and may be appropriately determined depending on the nature of each material. It is generally preferred to add the flaky titanic acid to the dispersion medium and then add the third component.

Next, a seventh invention of the present invention comprises at least the resin composition of the flaky titanic acid of the present invention. Examples of the resin composition include a plastic resin composition, a coating composition, and an ink composition.

The plastic resin used in the present invention is, for example, the following, and is not particularly limited. In addition, two or more of the following resins may be used in combination for the purpose of improving physical properties such as scratch resistance, scratch resistance, chemical resistance, and fluidity.

As the thermoplastic resin, an example is as follows:
(1) General-purpose plastic resin ((a) polyolefin resin (polyethylene, polypropylene, etc.), (b) polyvinyl chloride resin, (c) acrylonitrile butadiene styrene resin, (d) polystyrene resin, (e) methacrylic resin, (f) polyvinylidene chloride resin, etc.)
(2) Engineering plastic resin ((a) polycarbonate resin, (b) polyethylene terephthalate resin, (c) polyamide resin, (d) polyacetal resin, (e) modified poly Phenylene ether, (f) fluororesin, etc.)
(3) Super engineering plastic resin ((a) polyphenylene sulfide resin (PPS), (b) polyfluorene resin (PSF), (c) polyether oxime resin (PES), (d) amorphous polyarylate resin (PAR), (e) liquid crystal polymer (LCP), (f) polyetheretherketone resin (PEEK), (g) polyamidoximine resin (PAI), (h) polyether fluorene imine resin ( PEI)) and so on.

The blending ratio of the flaky titanic acid to the plastic resin is not particularly limited, but is usually in the range of 1 to 80 parts by mass, more preferably 1 to 60 parts by mass, per 100 parts by mass of the plastic resin. In the case of a master batch, it is in the range of 10 to 900 parts by mass, more preferably in the range of 50 to 500 parts by mass. Further, depending on the application, those skilled in the art can add reinforcing materials such as known glass fibers, or various additives such as stabilizers, dispersants, lubricants, antioxidants, ultraviolet absorbers, and fillers.

These resin compositions can be obtained by blending the above-mentioned flaky titanic acid with a melted resin using a kneader. The kneading machine is generally used by a user, and examples thereof include a one-shaft extruder, a two-axis extruder, a dense mixer such as a Bunbury mixer, and a roll forming machine.

The flaky titanic acid blended resin composition obtained by the kneading machine can be molded by a known method. In particular, by performing the method of applying a load such as flaky titanic acid in the alignment resin, the glittering property due to the flaky titanic acid can be improved. As such a molding method, for example, blow molding can be mentioned. Further, the molded article can be heated and extended. Even by this method, the brightness due to the flaky titanic acid can be improved.

The coating composition or the ink composition of the present invention contains at least the above-mentioned flaky titanic acid, a resin component, and a solvent. Examples of the resin component include an alkyd resin, an acrylic resin, a polyester resin, an epoxy resin, an amine resin, a fluorine resin, a polyoxyn resin, and a urethane resin. A vinyl resin or the like is appropriately selected. The resin component is not particularly limited to an organic solvent-dissolved type, a water-soluble type, or a latex type, and the curing method is not limited to a heat curing type, a room temperature curing type, an ultraviolet curing type, or an electron beam curing type. The solvent may, for example, be an organic solvent such as an alcohol, an ester, an ether, a ketone, an aromatic hydrocarbon or an aliphatic hydrocarbon, water or a mixed solvent thereof, and the solvent is selected depending on the suitability of the resin component. Other coloring agents, extenders, surfactants, plasticizers, hardening aids, dryers, defoamers, tackifiers, emulsifiers, flow regulators, including organic pigments, inorganic pigments, dyes, etc., depending on the purpose , anti-skinning agents, anti-fading agents, UV absorbers, anti-fungal agents and other additives, fillers, etc. These raw materials can be blended in a known manner to form a coating composition or an ink composition. Alternatively, the curing agent, the curing aid, and the curable resin component may each be used as a hardening liquid as a two-component coating material which is used in combination at the time of coating.

The coating composition of the present invention can be applied to the object to be coated by a known method to obtain a coating film. Specifically, spin coating, spray coating, roll coating, dip coating, flow coating, knife coating, electrostatic coating, bar coating, die coating, brush coating, dropping of droplets, etc. can be used without limitation. . The apparatus used for coating the coating composition can be appropriately selected from known apparatuses such as a spray gun, a press roll, a bristles, a bar coater, and a doctor blade.

The coating method is not particularly limited, and the predetermined film thickness may be applied once, or may be applied in multiple layers to form a predetermined film thickness. When the wet film thickness is relatively thin, the motility (prone) of the flaky titanic acid is restricted, and it is easy to be aligned with the coating film. According to this, in order to apply a coating method of a predetermined film thickness by laminating a plurality of times, it is preferable to improve the alignment degree of the flaky titanic acid and to further improve the glossiness of the coating film. The number of coatings is preferably from 2 to 15 times, more preferably from 4 to 10 times, from the viewpoint of lightness and economy.

[Examples]

Although the invention is illustrated in more detail by the following examples, the invention is not limited to the examples.

(Example 1)
Titanium oxide (titanium oxide A-100 manufactured by Ishihara Sangyo Co., Ltd.), potassium carbonate and lithium carbonate (all manufactured by Kanto Chemical Co., Ltd.) were thoroughly mixed in an agate mortar at a mass ratio of 100:40:9.2, and then burned at 1150 ° C in the atmosphere. Lithium potassium titanate (K _0.8 Li _0.27 Ti _1.73 O ₄ ) of an orthorhombic fibrite structure was synthesized in 5 hours. The obtained lithium potassium titanate was pulverized in an agate mortar to obtain a lithium titanate potassium powder.

The lithium potassium titanate powder obtained by mixing was mixed with a four-fold by mass 1.1 aqueous sulfuric acid solution for 30 minutes to carry out ion exchange to form a layered titanic acid. The obtained layered titanate solid was filtered and washed to obtain a layered titanate block. The amount of potassium contained in the layered titanate block was analyzed by a fluorescent X-ray analyzer (manufactured by Rigaku Corporation, RIX 2100), and it was 0.25% as K ₂ O/TiO ₂ .

The obtained layered titanate block was again dispersed in pure water in a form of 100 g/L in terms of TiO ₂ to obtain a layered titanic acid dispersion. After mixing the layered titanic acid dispersion with aqueous ammonia to adjust the pH to 7.3, 21.4 g of 2-amino-2-methyl-1-propanol 90% aqueous solution was added relative to 100 g of TiO ₂ (relative to The hydrogen ion contained in the layered titanic acid was 0.3 neutralizing equivalent), and the mixture was stirred at room temperature for 1 hour to obtain a flaky titanic acid dispersion. The pH of the flaky titanic acid dispersion was 10.5.

Next, a sieve having a mesh distance of 45 μm was installed in a slurry classifier (SS95×250 manufactured by ACO JAPAN Co., Ltd.), and the obtained flaky titanic acid dispersion was diluted twice with pure water to flow at 30 L/hour, respectively. The flaky titanic acid dispersion on the web and the flaky titanic acid dispersion under the net are recovered. Next, the sieve hole was changed to a mesh distance of 20 μm, and the flaky titanic acid dispersion liquid which was obtained by the classification of 45 μm was flowed at 20 L/hour to recover the flaky titanic acid dispersion on the net (indicated as flaky titanium). The dispersion in the acid sieve) and the flaky titanic acid dispersion under the net.

The flaky titanate sieve dispersion, that is, the flaky titanic acid dispersion having a mesh size of 20 μm or more and 45 μm or less, was centrifuged at 10,000 rpm for 10 minutes to obtain a flaky titanate block. Next, pure water was added to the flaky titanate block to prepare a slurry having a solid content of 8%. This slurry was spray-dried under the conditions of an inlet temperature of 190 ° C and an outlet temperature of 85 ° C using a spray dryer (manufactured by Okawara Chemical Co., Ltd., L-8i) to obtain a flaky titanic acid powder.

(Example 2)
The addition amount of the 2-amino-2-methyl-1-propanol 90% aqueous solution of Example 1 was 10.7 g with respect to 100 g of TiO ₂ (0.15 based on the hydrogen ion contained in the layered titanic acid). The flaky titanic acid dispersion, the flaky titanate sieve dispersion, the flaky titanate block, and the flaky titanic acid powder were obtained in the same manner as in Example 1 except for the neutralization equivalent.

(Example 3)
The layered titanate block was obtained by ion exchange in the same manner as in Example 1 except that the amount of the sulfuric acid aqueous solution specified in 1.1 for ion exchange was adjusted. The amount of potassium contained in the layered titanate block was analyzed by a fluorescent X-ray analyzer (manufactured by Rigaku Corporation, RIX 2100), and it was 3.3% as K ₂ O/TiO ₂ .

The obtained layered titanate block was again dispersed in pure water in a manner of 8.5% in terms of TiO ₂ to obtain a layered titanic acid dispersion. After mixing the layered titanic acid dispersion with aqueous ammonia to adjust the pH to 8.7, 21.4 g of 2-amino-2-methyl-1-propanol 90% aqueous solution was added relative to 100 g of TiO ₂ (relative to The hydrogen ion contained in the layered titanic acid was 0.3 neutralizing equivalent), and the mixture was stirred at room temperature for 1 hour to obtain a flaky titanic acid dispersion.

Next, a sieve having a mesh distance of 10 μm was installed in a slurry classifier (SS95×250 manufactured by ACO JAPAN Co., Ltd.), and the obtained flaky titanic acid dispersion was diluted twice with pure water to carry out classification at 18 L/hour. The flaky titanic acid dispersion on the net and the flaky titanic acid dispersion under the net are separately recovered.

The flaky titanic acid dispersion on the net was diluted 3 times with pure water, and separated into a precipitate and a supernatant by a centrifugal separator (Mitsubishi Chemical Mechanism, SJ10F). The precipitate obtained by centrifugation (flaky titanate block) was spray-dried using a spray dryer (L-8i manufactured by Okawara Chemical Machinery Co., Ltd.) at an inlet temperature of 190 ° C and an outlet temperature of 85 ° C. A flaky titanate powder was obtained.

(Comparative Example 1)
In the same manner as in Example 1, except that the flaky titanic acid dispersion obtained in Example 1 was not subjected to the classification operation, centrifugation, slurry preparation, and spray drying were carried out to obtain a flaky titanate block. , flaky titanic acid powder.

(Comparative Example 2)
In the same manner as in Example 2, except that the flaky titanic acid dispersion obtained in Example 2 was not subjected to the classification operation, centrifugation, slurry preparation, and spray drying were carried out to obtain a flaky titanate block. , flaky titanic acid powder.

(Comparative Example 3)
In addition to the calcination temperature at the time of synthesizing lithium potassium titanate, the temperature was set to 1100 ° C, and as the release agent, 3.5 g of n-propylamine relative to 100 g of TiO ₂ was used (the hydrogen ion contained in the layered titanic acid was 0.08). The flaky titanic acid dispersion liquid was obtained in the same manner as in Example 1 except that the neutralization equivalent was used. This flaky titanic acid dispersion liquid was centrifuged at 10,000 rpm for 10 minutes, and the solid component was collected to obtain a flaky titanate block.

(Measurement of particle size distribution)
The particle size distribution of the flaky titanic acid in the flaky titanic acid dispersion was measured using a laser diffraction/scattering particle diameter distribution measuring apparatus (manufactured by Horiba, Ltd., LA-950). The refractive index is 2.50. The flaky titanate sieve dispersions classified in Examples 1 and 2 were used for measurement, and in Example 3, the flaky titanic acid dispersion on the network after classification was used for measurement.

(Measurement of carbon and nitrogen)
The amount of carbon and the amount of nitrogen of the sample after the sheet-like titanate block was dried at 150 ° C for 16 hours were analyzed using an elemental analyzer (Vario EL III manufactured by Elementar Co., Ltd.).

(production of paint 1)
1.25 g of the flaky titanic acid powder obtained in Examples 1 and 2, Comparative Examples 1 and 2, 11.9 g of the blended yttrium acrylate resin (solid content 42%), and 9.40 g of pure water were placed in Table 1. The glass container was mixed with a paint shaker for 5 minutes to prepare a paint. The flaky titanate block obtained in Comparative Example 3 was weighed in a solid content of 1.25 g, and the blended acrylic ruthenium resin blend (solid content: 42%) of Table 1 was 11.9 g, and pure water was 9.40 g (including The flaky titanate block was kept in a glass container and mixed with a paint shaker for 5 minutes to prepare a coating. The solid content of the flaky titanate block was calculated from the mass change before and after drying at 150 ° C for 16 hours.

(production of paint 2)
5.0 g of the flaky titanic acid powder obtained in Examples 1, 2, and 3, Comparative Examples 1 and 2, and 11.9 g of the blended acrylic acid bismuth resin blend (solid content 42%) of Table 1 were placed in a glass container. After mixing for 5 minutes with a paint shaker, pure water was added so that the viscosity of the coating became 200 mPa·s to prepare a coating. The flaky titanate block obtained in Comparative Example 3 was weighed in a solid content of 5.0 g, and 11.9 g of the blended acrylic ruthenium resin blend (solid content 42%) of Table 1 was placed in a glass container to paint The mixture was mixed for 5 minutes, and pure water was added so that the viscosity of the coating became 200 mPa·s to prepare a coating. The solid content of the flaky titanate block was calculated from the mass change before and after drying at 150 ° C for 16 hours.

(Production of Coating Film 1 for Brightness Evaluation)
The coating prepared by the method of "Production of Coatings 1" was applied to a PET film (Lumirror T60, manufactured by Toray Industries, Inc.) using a 3 mil doctor blade, and forced drying was carried out at 60 ° C for 30 minutes to produce a glittering property. Evaluation coating film. In addition, the coating film of the commercially available pearl mica (Iriodin 6103 and Iriodin 6111 manufactured by Merck & Co., Ltd.) was produced in the same manner as the reference pigments 1 and 2, respectively, as a light feeling and a dense feeling, which will be described later. Evaluation criteria for a 3-stage assessment of each visual assessment of particle sensation.

(Production of Coating Film 2 for Brightness Evaluation)
The coating prepared by the method of the "Production of Coatings 2" was applied to a PET film (Lumirror T60, manufactured by Toray Industries, Inc.) by a spray gun, and forced drying was carried out at 60 ° C for 30 minutes to prepare a film thickness of 10 μm. Coating film.

(Evaluation of Shadow Sense 1)
The back surface of the coating film produced by the method of "manufacturing of the coating film 1 for the evaluation of the brightness evaluation" is applied to the black background of the black and white chart paper, and the variable angle spectrophotometry system (manufactured by Murakami Color Research Co., Ltd., GCMS-) is used. Type 3), the light source was irradiated from -45°, and the L ^* value of the bright spot (light-receiving angle 40° and light-receiving angle 50°) and shadow (light-receiving angle -65°) were measured. Shadow subtracted from the maximum highlight of calculating an L ^* L ^* ΔL ^* _1, evaluation shading appearance.

(Evaluation of Shadow Sense 2)
The back surface of the coating film produced by the method of "manufacturing the coating film 2 for evaluating the brightness evaluation" is applied to the white background of the black and white graphic paper, and the light source is used by a multi-angle colorimeter (BYK-mac i, manufactured by Biggardner Co., Ltd.). The L ^* value of the bright spot (light-receiving angle 30°) and the shadow (light-receiving angle -65°) were measured by irradiation from -45°. Highlights from the shadow of the L ^* L ^* minus the value set at ΔL ^* _2, assess the shadows sense.

(evaluation of the sense of light)
The brightness of the produced film was visually evaluated. The term "brightness" refers to an index indicating the degree of luminance of a metallic hue, and is evaluated in three stages of 1-3 from the order of strong lightness.

(Evaluation of silky feeling (compactness, particle sensation))
The silky feel of the produced coating film was visually evaluated. As an indicator of the silky feeling, it is defined as two types of dense feeling and particle feeling. The so-called dense feeling refers to the smooth design without seams like a scorpion, which is evaluated from the stage of 1 to 3 in order of denseness. The particle sensation refers to a design in which the particles are individually glittering, and the one who does not feel the particle sensation is set to 1, and the person who has a strong sensation of sensation is set to 3, and is evaluated in three stages of 1-3.

(particle thickness measurement)
The coating film prepared for the evaluation of the glittering property was cut by a microtome, and the cross section was observed with a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, S-4800). The thickness of 50 pieces of the flaky titanic acid particles observed was measured, and the average value was made into the thickness of the flaky titanic acid particle.

(Production of coating film for weather resistance evaluation)
The coating material was applied to a matte steel plate using a No. 60 bar coater and forced to dry at 60 ° C for 30 minutes to form a glittering coating film. Next, a main component and a curing agent of a commercially available two-liquid-curing urethane resin coating were mixed to prepare a top coat. This coating material was applied onto the above-mentioned bright coating film using a No. 60 bar coater, and was forcibly dried at 80 ° C for 30 minutes to form a top coat as a coating film for weather resistance evaluation.

(Evaluation of weather resistance)
The L, a, and b values of the coating film's characteristic system were measured using a spectrophotometer (manufactured by Nippon Denshoku Industries Co., Ltd., SD 5000). The weatherability of the film is evaluated by an accelerated exposure test. The test was carried out using a sunlight weatherproof test chamber (Suga test mechanism, WEL-SUN-HC type) at a black panel temperature of 63 ± 3 ° C, a light source carbon arc lamp, and a shower spray for 12 minutes in one hour. The L, a, and b values were measured in the same manner as described above for each predetermined period of time. The color difference ΔE was calculated from the values of L, a, and b after 300 hours of accelerated exposure and the values of L, a, and b before the accelerated exposure test. Calculated as ΔE = [(ΔL) ² + (Δa) ² + (Δb) ² ] ^(1/2) .

(analysis of Cs content)
The flaky titanic acid powder was analyzed by a fluorescent X-ray analyzer (manufactured by Rigaku Corporation, RIX 2100) to determine the Cs content.

The particle size distribution measurement results of the examples and comparative examples are shown in Table 2. Table 3 shows the results of evaluation of ΔL ^* ₁ (and ΔL ^* ₂ ), glossiness, and silky feel. The thickness of the flaky titanic acid particles of Example 1 was 0.1 μm, the thickness of the flaky titanic acid particles of Comparative Example 1 was 0.1 μm, and the thickness of the flaky titanic acid particles of Comparative Example 3 was 0.7 μm. The amount of Cs of the flaky titanic acid powder obtained in Example 1 was the lower limit of detection (0.01% by mass) or less.

In the samples of Examples 1 and 2 and Comparative Examples 1 and 2, ΔL ^* _{1 was} 150 or more (ΔL ^* ₂ was 60 or more), and although there was a feeling of shadow and brightness, (D90-D10)/D50 was performed by the classification operation. In Examples 1 to 3 which were set to 1.5 or less, the silky feel was excellent as compared with Comparative Examples 1 and 2. In Comparative Example 3, ΔL ^* ₁ (and ΔL ^* ₂ ) was low and the sense of shadow and brightness were lacking. Moreover, the silky feeling confirmed by visual observation was the lowest. As a reference example, as shown in the figure, it is understood that the commercially available pearl mica does not have both a glossy feeling and a silky feel, but the flake-shaped titanic acids of Examples 1 to 3 not only have a light feeling and a shadow, but also exhibit a dense feeling. High and almost unique sense of design.

The carbon amount, the basic functional group content, the nitrogen amount, and the weather resistance (ΔE) of each sample are shown in Table 4. The basic functional group content (%) of Example 1 using 2-amino-2-methyl-1-propanol as a release agent, (the number of basic functional groups per molecule of the basic organic compound) × (carbon amount (% by mass)) / {(amount of atomic carbon × number of carbon atoms per compound) / (quantity of TiO ₂ )}, the general formula is 1 × (0.910) / {(12.0 × 4) / 79.9}=1.51%. The basic functional group content (%) of Comparative Example 3 using n-propylamine as a release agent, (the number of basic functional groups per molecule of basic organic compound) × {(carbon amount (% by mass)) / (amount of carbon atom × number of carbon atoms per compound)} / (a formula of TiO ₂ ) The general formula is 1 × (1.11) / {(12.0 × 3) / 79.9} = 2.46%.

In Examples 1 to 3, the content of the basic functional group was reduced to 2.4% or less by a classification operation, and the ΔE was low as compared with the comparative example, and the weather resistance was improved. The comparative examples all have a basic functional group content of more than 2.4%, and weather resistance is not sufficient.

[Industrial availability]

According to the present invention, it is possible to provide a flaky titanic acid which is excellent in glossiness and has a silky feeling of a shadow, and which exhibits high weather resistance, and which is inexpensive and suitable for industrial production. Further, it is possible to further impart a smooth feeling to the coating film by improving the dense feeling and reducing the feeling of the particles. Accordingly, the flaky titanic acid of the present invention is suitably used as a bright pigment, and can be blended in a coating composition, an ink composition, a plastic resin composition or the like. Thereby, it is possible to provide an article having a unique design feeling that has not been used in the past.

Claims (13)

A flaky titanic acid comprising a basic organic compound having a basic functional group content of 2.4% or less, and a variable angle colorimetric value ΔL ^* ₁ as a coating film of 150 or more. A flaky titanic acid comprising a basic organic compound having a basic functional group content of 2.4% or less, and a variable angle color measurement value ΔL ^* ₂ as a coating film of 60 or more. A flaky titanic acid in a volumetric particle size distribution measured by a laser diffraction/scattering method, the cumulative 10% particle diameter is represented by D10, the median diameter is represented by D50, and the cumulative 90% particle diameter is represented by D90. When (D90-D10)/D50 is 1.5 or less. A method for producing flaky titanic acid, comprising flaky titanic acid having an alkaline organic compound which is present between layers and/or surfaces, and having a volume particle size distribution (D90-D10)/D50 of 1.5 or less The steps. A method for producing a flaky titanic acid, which comprises the step of separating a layer of a layer of titanic acid having a (D90-D10)/D50 of 1.5 or less with a basic organic compound in a volume particle size distribution. A method for producing a flaky titanic acid, comprising the steps of: obtaining a layered titanic acid by contacting a metal salt of a titanate having a (D90-D10)/D50 of 1.5 or less with an acidic compound in a volume particle size distribution; The step of stripping the layer of the above-mentioned layered titanic acid with a basic organic compound. The method for producing flaky titanic acid according to any one of claims 4 to 6, further comprising a flaky titanic acid containing a basic organic compound at a pH of 6 or more The step of water under 10 medium. A bright pigment comprising the flaky titanic acid according to any one of claims 1 to 3. A dispersion liquid containing at least the flaky titanic acid described in any one of claims 1 to 3 and a dispersion medium. A resin composition comprising at least the flaky titanic acid and a resin according to any one of claims 1 to 3. A coating composition comprising at least the flaky titanic acid and a resin according to any one of claims 1 to 3. A plastic resin composition comprising at least the flaky titanic acid and a plastic resin according to any one of claims 1 to 3. An ink composition comprising at least the flaky titanic acid according to any one of claims 1 to 3, a resin, and a solvent.